Itaconic acid esters of 1,2 alkane ketals



United States Patent 3,225,015 ITACONIC ACID ESTERS OF 1,2 ALKANE KETALS Gaetano F. DAlelio, South Bend, Ind., assignor to Scott Paper Company, Philadelphia, Pa., a corporation of Pennsylvania N0 Drawing. Filed July 9, 1962, Ser. No. 208,593

18 Claims. (Cl. 260-784) This invention is concerned with new monomeric esters of itaconic acid and polymers and copolymers derived therefrom. Specifically it relates to itaconic esters of the general formula CH=CCOO- if 2 1'42 R' on2co0- in which R represents H, a saturated aliphatic hydrocarbon radical, an olefinic unsaturated hydrocarbon radical, said radicals containing one to eight carbon atoms, and R; R represents an alkylene dioxolane radical of the structure wherein n is an integer having a value of one to four and R represents an alkyl radical containing one and two carbon atoms, e.g., methyl and ethylradicals. The new monomeric esters of this invention are the itaconic acid esters of the alpha, beta cyclic ketals of alpha, beta, omega alkane triols containing three to six carbon atoms in the alhane chain having the formula HO(OH2)nCHCH2 O O RII C RII wherein n is an integer having a value of one to four. Thus, the new monomers of this invention are the itaconic esters of the 1,2 ketals of 1,2,3 propane triol; 1,2,4 butane triol; 1,2,5 pentane triol; and 1,2,6 hexane triol.

Itaconic acid is a dicarboxylic acid, and accordingly monoand di-esters of the alcohols HO(CH2)nCHOH o\ /0 RII C RI/ can be prepared and utilized in the practice of this invention.

Because of the commercial availability and other economic factors, the itaconic esters of 1,2 ketal of 1,2,3 propane triol, corresponding to the formula CHzOHCH mood-J Illustrative examples of the "ice The esters of this invention can be prepared by a number of methods. One convenient method is to use itaconic anhydride and the desired alcohol in accordance with the reaction This esterification reaction using the anhydride may be performed simply by melting together the two reactants; but preferably to avoid ketone elimination or other side reactions, the esterification is performed in an inert solvent such as heptane, hexane, benzene, toluene, diox ane, tetrahydrofurane, etc., and isolating the product. The monoester thus formed can be used as such for the preparation of polymers and copolymers, or may be used as an intermediate in the preparation of diesters by conversion to an alkali metal salt, such as the sodium, potassium, lithium salt, etc., and reacting the salt with a di-alkylsulfate, thus R R, nsoiNa B200 0 The new esters of this invention can be prepared also from itaconic acid, or the lower alkyl esters thereof, and the cyclic ketal of the alkane triol desired in accordance with the general reaction:

HO (onanoncn, oH,=o-o 0 o R 0 O moooP- i The specific method used in the preparation of the monomer depends in most cases on the monomer desired; for example, when the acid monoester is desired, the method using the anhydride is preferred; when a symmetrical diester is desired then either the acid dichloride or the dimethyl or the diethyl ester is reacted with the cyclic ket-al of the alkane triol, and when a mixed ester, that is, an itaconic ester containing a lower alkyl group to gether with the cyclic ketal ester group is desired, then the lower alkyl monoester acid chloride, or a lower alkyl diester is reacted with the cyclic ketal of the triol as indicated in the reactions hereinabove.

The esters of this invention are polymerizable monomers possessing a polymerizable CH =C structure and may be polymerized to form homopolymers, or copolymers from a mixture of two or more of these esters, or copolymers from one or more of these new esters with other monomers containing a vinyl, CH =CH, a vinylidene, CH =C or a vinylene group,

Z|1H=CIlH Illustrative examples of other monomers containing such groups are the acrylic esters such as methyl acrylate, ethyl acrylate, hexyl acrylate, allyl acrylate, phenyl acrylate, benZyl acrylate, methyl-alpha-chloroacrylate, etc; the methacrylic esters such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, methallyl methacrylate, ethylene dimethacrylate, etc.; the vinyl esters such as vinyl chloride, vinyl acetate, vinyl stearate, vinyl benz-oate, vinyl chloroacetate, divinyl phthalate, divinyl succinate, etc; the polymerizable amides and nitriles such as acrylamide, hydroxymethylacrylamide, methacrylamide, itaconic monoamides, itaconic diamide, acrylonitrile, methacrylonitrile, etc.; the alkenyl aryl compounds such as styrene, o-methyl styrene, p methyl styrene, alphamethyl styrene, the chloro-styrenes, divinyl benzene, diallyl benzene, etc.; the monoand polyallyl esters such as allyl acetate, diallyl succinate, diallyl phthalate, diallyl maleate, diallyl fumarate; the vinylidene compounds such as vinylidene chloride, vinylidene cyanide, methylene maloni'c esters, etc. vinylene compounds such as vinylene carbonates, maleic anhydride, maleic monoesters and maleic diesters; the itaconic compounds such as itaconic anhydride, the itaconic monoand the itaconic diesters of the lower and higher aliphatic alcohols; the dienes such as butadiene, isoprene, 2-chloro-butadiene 1,3 etc. The proportion of the new monomers in copolymers with other monomer will depend, in accordance with the accepted principles of copolymerization, on the reactivity and selectivity constants, r and r of the co-monomers used in preparing the copolymer, the ratio of the monomers used and the extent of conversion. However, by selecting appropriate conditions for the copolymerization, copolymers, using the new monomers of this invention, can be made to contain effective and small amounts of these new monomers, for example, of the order of from 0.1% to 0.5% to very high amounts of the order of 99.5% to 99.9% in the final polymer products.

The new monomers of this invention can be polymerized by the known methods used to polymerize acrylic, methacrylic or itaconic monomeric compounds. The new monomers, in the presence or absence of other polymerizable C=C containing monomers, can be polymerized in bulk, solution, emulsion, or suspension with or without polymerization initiators and other modifiers. As polymerization initiators there can be used the per-compounds, such as potassium persulfate, tertiary butyl peracetate, benzoyl peroxide, cumene hydroperoxide, tertiary butyl peroxide, tertiary butyl perbenzoate, hydrogen peroxide with or without ferrous salts, etc.; the azo catalysts such as alpha,alpha'azobis (isobutyronitrile), ultraviolet light in the absence or presence of ketones, ionizing radiation from X-rays, electron and particle accelerators, cobalt 60 sources, etc.

In solution polymerization the medium can be selected from solvents which retain the polymer in solution throughout the polymerization, or can be chosen so that the polymer precipitates when formed and can be selected from the class of aliphatic, cycloaliphatic and aromatic hydrocarbons, esters, ethers, ketones, halogenated hydrocarbons, etc., or mixtures thereof depending on the form in which the polymer is desired. When halogenated hydrocarbons are used they also act as modifiers of the polymerizations. In emulsion polymerization, the emulsifying agent to be used in the aqueous system is selected from the class of fatty acid soaps, salts of sulfonated alkyl benzenes, polyvinyl alcohol, gelatin, polyacrylic acid, salts of styrene-maleic acid polymers, gelatin and the like, which can be used alone or with buifering agents such as sodium acetate, borax, trisodium phosphate and the like. In suspension polymerization, the dispersion agent can be selected from the class of insoluble inorganic carbonates, phosphates and silicates to be used alone or in the presence of minor amounts of deflocculating agents such as sodium dodecylbenzene sulfonate or potassium stearate.

The new monomers and polymers of this invention have new and valuable properties which are attributable to the cyclic ketal structure. The monomers of this invention have a high absorption in the ultraviolet light region, that is, the UV transmission is very low in the region of 500 to 5000 Angstroms. This absorbed energy, corresponding from about 4.1 to about 40 electron volts, produces secondary effects, which are useful in producing cr-osslinked polymers.

While the exact mechanism is not exactly understood it is believed that the ultraviolet radiation generates radicals in the system by opening the ketal ring, thus and that these radical structures are responsible for the cross-linking. In photochemical reactions of this type normally one pair of radicals is generated for each photon absorbed. However, due to other reactions the quantum yield may be reduced to 0.5 or even less. The reactivity of the compounds of this invention is readily observable.

When monomeric methyl acrylate is polymerized for one hour with a UV. source from a mercury lamp emitting 17,000 photons per hour, only a soluble fusible polymer is obtained, whereas if a monomeric mixture of 80 parts of methyl acrylate and 20 parts of that homopolymers of the normal alkyl esters of itaconic 1 acid are not as responsive to U.V. light as the itaconic esters containing the ketal structures of this invention.

The following examples illustrate the synthesis of the monomers, polymers, and copolymers of this invention, and are not given by way of limitation but by way of illustration. The parts and percentages given are parts and percentages by weight unless otherwise specified.

EXAMPLE I There were combined in 200 parts of benzene, 28.0 parts of itaconic anhydride and 34.0 parts of glyceryl ketal,

HOCHzOHCHB CHsCCH in a reaction vessel equipped with stirrer, condenser, and heating means, and the mixture heated at 60 C. for 48 hours, or at reflux for hours following which it is cooled to room temperature. The desired ester on evaporation of the solvent under reduced pressure remains as a colorless or light colored oil in an almost quantitative yield and on standing crystallizes the ester product, on recrystallization from ether, has a m.p. of 66-68" C.

Elemental analysis for C and H gives values of 53.8% and 6.4% respectively, which is in excellent agreement with the calculated values of 54.1% and 6.56% respectively, for the compound, 4-(2,Z-dimethyl-dioxalone-1,3) methylene hydrogen itaconate corresponding to the formula of orn=oooorr CHzCOOCHzCHCHr o\ /0 CHa-CCH3 EXAMPLE II The procedure of Example I is repeated using an equivalent amount of the 1,2 ketal of 1,2,6 hexanetriol instead of glyceryl ketal, and there is obtained an itaconate represented by the formula which on analysis for C and H and acid number determination give values in close agreement with the theoretical values for the compound.

EXAMPLE III In a well-stirred reaction vessel containing 200 parts of benzene and 24.4 parts of the monomer of Example I is added 4.0 parts of NaOH in 50 parts of ethyl alcohol to form the sodium salt. To this mixture is added slowly over a period of one hour 12.6 parts of dimethyl sulfate and the mixture heated at 6070 C. for two 'hours, following which it is allowed to cool at room temperature and filtered to remove, solid salts. The benzene solution is washed with dilute aqueous sodium carbonate solution and with distilled water until neutral; then dried with anhydrous sodium sulfate which is removed by filtration. The benzene solution containing the crude product is treated with activated carbon, filtered and concentrated at a reduced pressure of 15-30 mm., leaving the ester as a colorless viscous oil, distillation of which is not possible without the pyrolytic elimination of CH COCH and other products. Elemental analysis of the viscous oil gives values of 55.32% C. and 6.89% H, which is in good agreement with the calculated values of 55.81% C. and 6.95% H for the compound CHz=C-C o 0 CH3 HzCOOCHzCHCHz 0\ /o CH3C-CH3 When an equivalent amount of diethyl sulfate is used instead of dimethyl sulfate in this procedure, then the cone sponding ethyl ester is obtained, as

CHg=C-C o o 02H,

CHZCOOCHQCHC\H2 CH -C-CHa EXAMPLE IV To a reaction vessel equipped with stirrer, condenser and inlet containing 1600 parts of benzene, 264 parts of glyceryl ketal, and 205 parts of triethyl amine and cooled to 05 C. is slowly added over a period of five hours 167 parts of fumaryl chloride in parts of benzene, following which the reaction mixture is allowed to come to room temperature during a period of five hours. The mixture is filtered to remove (CH N.HCl and the filtrate washed with dilute aqueous Na CO solution until slightly alkaline and then with distilled water until neutral. The benzene solution of the ester is dried overnight with anhydrous Na CO filtered and the filtrate separated from benzene by distillation under reduced pressure, leaving a clear viscous oil which cannot be distilled at 10 mm. without evidence of the pyrolytic elimination of CH COCH and other products. Elemental analysis of the residual oil gave values for C and H of 56.8% and 7.18% respec tively, which is in good agreement for the calculated values of 57.03% C. and 7.26% H for the compound o 0 0H2=G-ooooHz HO Hz hmoooomortom CHa CCHs When the glyceryl ketal of this example is replaced by an equivalent amount of the homologous ketals, such as HO(CH2)4CHOH2 HOCHzCHCHi CH3CCH3 CHQ OZCZH5 and HOCHzCHCI-Ig CQH5 C CZH5 then the corresponding itaconic diesters are obtained.

EXAMPLE V To a reaction vessel equipped with a stirrer, condenser, and inlet is added 1000 parts of toluene, 112 parts of itaconic anhydride, and 130 parts of octyl alcohol and the mixture reacted at reflux for five hours to produce the octyl hemi-itaconate,

To the reaction mixture then is added 119 parts of thionyl chloride and reflux continued until S and HCl are no longer liberated from the reaction, leaving CHz=CCOCl CHQCOOCSH" in solution. The reaction solution is cooled to C., and there is added slowly over a period of five hours a mixture of 101 parts of triethyl amine and 133 parts of glyceryl ketal in 200 parts of ethyl ether, following which the mixture is allowed to come to room temperature. The mixture is then filtered to remove (CH N.HCl, washed and dried according to the procedure of Example IV, after which the solvent is removed by distillation under reduced pressure, leaving a clear viscous oil which is not distillable at 5 mm. pressure without evidence of pyrolytic eliminations. Elemental analysis for carbon and hydrogen gives values of 63.94% and 8.94% respectively, which is consistent with the formula cm7o om O O CH=C-COOOHOHCH2 CHZCOOOSHU When an equivalent amount of allyl or methallyl alcohol is used in the procedure of this example, instead of Styrene and the itaconyl ester of glyceryl ketal, were mixed in the mole ratios 04:1, 05:1, 0.621, 0.86:1, 1:1, 3:1, 7 :1, 10:1, and :1 respectively, and sufiicient purified acetone added to produce a solution of monomers in solvent. The mixtures were polymerized at C. for 72-96 hours using an amount of benzoyl peroxide equivalent to 0.25% by weight of the monomer as the catalyst, following which they are precipitated by addition of the solution to methanol, isolated by filtration, and dried. The copolymers obtained from these various ratios were soluble in a variety of solvents such as acetone, dioxane, toluene, dimethyl formamide, dimethyl sulfoxide, ethylene carbonate, etc., and can be cast into clear colorless films; but when heated at elevated temperatures from 160200 C. for various periods of time, cross-linked polymeric compositions are obtained. When the clear unheated films are subjected to the ultraviolet radiation of a mercury lamp for 10-20 minutes, then insoluble films are obtained.

EXAMPLE VII Vinyl acetate and the itaconyl ester of glyceryl ketal are mixed in the mole ratios of 0.35:1, 0.5:1, 0.65:1, 0.90: 1, 1:1, 3:1, 7:1, 10:1, and 15:1 and sufiicient acetone added to produce a 20% solution of monomer in the solvent. The mixtures were polymerized at 5060 C.

using 1.25% of 2,2'azo-bis(isobutyronitrile) as the catalyst, and soluble, fusible polymers are obtained which can be crosslinked on heating and by exposure to ultraviolet light similarly to the polymers of Example VI.

EXAMPLE VIII Methyl acrylate and the itaconate are copolymerized in the mole ratios of the procedure of Example VI and colorless, curable copolymers are similarly obtained.

EXAMPLE IX Methyl methacrylate and the itaconate are copolymerized as in Example VIII and clear, colorless copolymers having properties related to the acrylate copolymers are obtained.

As illustrated by the range of ratios of the above various monomer pairs, copolymers of a wide limit of compositions can be readily prepared according to the standard procedures known in the art.

can be isolated from the toluene solution by precipitation with methyl alcohol.

EXAMPLE XI The following example illustrates an emulsion polymerization. Vinyl acetate parts, 10 parts of OH =CCOOC H HzCOOCHzCHCHz 0\ /0 CH3-CCH3 the monomeric ethyl ester of Example III, parts of water containing 1.5 parts of polyvinyl alcohol and 0.5 parts of potassium sulfate are heated in a suitable reactor at 7580 C. for 12 hours producing a latex which can be used directly as an adhesive.

EXAMPLE XII Thirty parts of CH=C-COOCH2CH=CH2 HZCOOCH2C|3H(|JH2 0\ /0 CH3,CCH3

the monomeric allyl ester of Example V, 1 part of benzoyl peroxide are mixed and heated at 80 C. for 24 hours, producing a thick viscous polymer which, on continued heating at 80 C. for 100 hours, becomes insoluble and infusible. The intermediate viscous polymer is suitable as a casting resin.

EXAMPLE XIII Five parts of methyl acrylate and 1.0 part of CHz=CC O O CH:

HzCOOCHzCHCHz 0 o CH COH3 are mixed and irradiated with U.V. light of a mercury lamp for four hours, and a polymer, insoluble in benzene, is obtained.

From the foregoing examples it may be seen that new monomers of this invention are quite versatile, their inherent characteristics enabling the production of a wide range of polymers and copolymers. By varying the conditions of polymerization, such as, the nature of the catalyst, as well as its concentration, the temperature of polymerization, the choice of the medium, if any, .in which the polymerization is performed, and the selection of, as well as the ratio of monomeric compounds employed, the physical and chemical properties of the ultimate polymer can be controlled. Additionally, as has been pointed out hereinabove these new monomers contain a CH :C grouping permitting polymerization by the regular procedures used in polymerizing acrylic, or itaconyl monomers; moreover, since they contain a cyclic ketal structure, they can undergo secondary reactions ultilizing the ketal ring independently of the CH ::C grouping. This secondary reaction may involve crosslinking of the monomeric structures but it is also possible for a ketone to be eliminated from the monomer on heating. In the absence of other reagents which modify the course of the reaction; the neutral esters of this invention such as begin to evolve ketones noticeably in the temperature range of ZOO-210 C., whereas if one of the carboXyl groups is left unesterified, for example as in CH;=OCOOH dHZOOOOHQCHCHi CH3C-CH3 the elimination is noticeable in the temperature range of 140-150 C.; and this reaction is probably due, and

favored by, the transesterification of the tree-COOH group with the cyclic ketal ring aw O\ /O CHa-C-CHS The variation in temperature required to effect crosslinking is carried into the polymers and copolymers of the monomers of this invention when they contain a free canboxylic group. This phenomenon is also observed when the carboxyl group is not part of the new monomer but is present as an element of a CH:C containing monomer such as acrylic acid, methacrylic acid, itaconic acid, itaconic acid monoester, maleic acid, fumaric acid, maleic acid monoester which has been copolymerized with the neutral, or di-esters of this invention. It was also discovered, in the use of the new monomers and polymers of this invention, that the temperature of ketone elimination could be greatly reduced in the presence of chemical modifiers such as acid and salts, for examples, H PO Na CO NaHCO ZnCl 10 FeSO etc. As illustrative of this improvement, the addition of 1% ZnCl to CH3-C-CH3 0 \O QH=C-OOOCH2HCH| JHQCOOCHrOHCHz 0 o CHa OCH can reduce the elimination temperature from about 200 C. to about C. These modifiers thereby increase the utility of the monomers and polymers of this invention by avoiding thermal pyrolysis of the compounds through lowering of the temperature required to produce a crosslinked polymer. Though the monomers of this invention are particularly useful in the preparation of polymers for the coating, laminating, and molding polymer arts, they are useful in themselves as photosensitizing agents to be added alone or with modifiers to other preformer polymers, as hydrohalide acceptors for polyvinyl halide type polymers and as chemical intermediates for reactions with amine, amides, and ureas.

It will be obvious that variations in the component elements of the newly discovered compounds, the manner of their preparation and utilization are possible without departing from the spirit of my invention or the scope of the appended claims.

What I claim is:

1. As new compounds, monomeric esters having the general formula mooo-T in which R is a member of the class consisting of hydrogen saturated and olefinic unsaturated aliphatic hydrocarbon containing from one to eight carbon atoms and R, and R represents -(CH2),,CHCH2 O RII CRII in which n is an integer having a value of from 1 to 4 inclusive, and R" is a member of the group consisting of methyl and ethyl radicals.

2. A monomer having the formula in which R is a member of the class consisting of hydrogen, saturated and olefinic unsaturated aliphatic hydrocarbons containing from one to eight carbon atoms and R, and R represents in which R is a member of the group consisting of methyl and ethyl radicals.

3. A monomer having the formula CHFC'C O OH JH C O O CHZCHCHZ CH CCHs 4. A monomer having the formula CHz=C-C o 0 CH3 H20 0 o OH3OHCH 1 1 5. A monomer having the formula CH3C-CH3 CH =C-O0oOH OHc H HzCOOCHaCHCQEa 6. The polymerization product of a claim 1.

7. The polymerization product claim 2.

8. The claim 3.

9. The claim 4.

10. The polymerization product of a monomer claim 5.

11. A copolymer of at least one monomer of claim 1 and at least one other compound containing a CH =C group.

12. A copolymer of at least one monomer of claim 2 and at least one other compound containing a CH =C group.

13. A copolymer of the monomer of claim 3 and at least one other compound containing a CH =C group.

14. A copolymer of the monomer of claim 4 and at least one other compound containing a CH =C group.

15. A copolymer of the monomer of claim 5 and at least one other monomer containing a CH =C group.

monomer of of a monomer of polymerization product of a monomer of polymerization product of a monomer of 16. The process of preparing a monomeric ester as defined in claim 1 which comprises reacting a compound of the formula wherein R is a member of the class of H, CH and C H wherein R is derived from an alcohol of the formula HO (CHghOHOHz References Cited by the Examiner UNITED STATES PATENTS 2,397,602 4/1946 Gresham 26078.4 2,680,735 6/1954 Fegley et al. 26086.3 3,010,923 11/1961 Ikeda 26078.4

JOSEPH L. SCHOFER, Primary Examiner.

DONALD E. CZAJA, Examiner. 

1. AS NEW COMPOUNDS, MONOMERIC ESTERS HAVING THE GENERAL FORMULA (R-)(R''-) (-OOC-CH2-C(=CH2)-COO-) IN WHICH R IS A MEMBER OF THE CLASS CONSISTING OF HYDROGEN SATURATED AND OLEFINIC UNSATURATED ALIPHATIC HYDROCARBON CONTAINING FROM ONE TO EIGHT CARBON ATOMS AND R'', AND R'' REPRESENTS (2,2-DI(R"-)-1,3-DIOXOLAN-4-YL)-(CH2)NIN WHICH N IS AN INTEGER HAVING A VALUE OF FROM 1 TO 4 INCLUSIVE, AND R" IS A MEMBER OF THE GROUP CONSISTING OF METHYL AND ETHYL RADICALS.
 6. THE POLYMERIZATION PRODUCT OF A MONOMER OF CLAIM
 1. 